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| United States Patent |
5,548,072
|
|
Dannheim
, et al.
|
August 20, 1996
|
Water-soluble phenyl azo aminoaphtol azo compounds containing a
fibre-reactive group of the vinylsulfone series and a
morpholino-fluorotriazinyl group, suitable as dyestuffs
Abstract
Water-soluble azo compounds, preparation thereof and use thereof as dyes
There are described monoazo compounds conforming to the formula (1)
##STR1##
which are used as dyes having fiber-reactive properties for preparing
strong, red, fast dyeings and prints on hydroxy- and/or
carboxamido-containing material, in particular fiber material, such as
wool and synthetic polyamide fibers and in particular cellulose fibers,
such as cotton.
In the formula (1):
M is hydrogen or an alkali metal; R.sup.1 is hydrogen or sulfo; R.sup.2 is
hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms,
sulfo, hydroxy, halogen or carboxy; R.sup.3 is hydrogen, halogen, alkyl of
1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms; Y is vinyl or is
ethyl which contains in the .beta.-position a substituent which is
eliminable with alkali to form a vinyl group; p is 1 or 2; the one
--SO.sub.3 M group is attached to the naphthalene ring para or meta to the
amino group.
| Inventors:
|
Dannheim; J org (Frankfurt am Main, DE);
Oehme; Dieter (Fl orsheim, DE);
Tappe; Horst (Dietzenbach, DE)
|
| Assignee:
|
Hoechst Aktiengesellschaft (Frankfurt, DE)
|
| Appl. No.:
|
462131 |
| Filed:
|
June 5, 1995 |
Foreign Application Priority Data
| Jun 17, 1993[DE] | 43 20 151.2 |
| Current U.S. Class: |
534/635; 8/549; 534/582 |
| Intern'l Class: |
C09B 062/085; C09B 062/51; D06P 001/38 |
| Field of Search: |
534/635
8/549
|
References Cited
U.S. Patent Documents
| 4649193 | Mar., 1987 | Meininger et al. | 534/635.
|
| 5097021 | Mar., 1992 | Stohr et al. | 534/635.
|
| 5233026 | Aug., 1993 | Tzikas | 534/635.
|
| Foreign Patent Documents |
| 0177445 | Sep., 1985 | EP.
| |
| 0308787 | Mar., 1989 | EP.
| |
Other References
European Search Report No. 94109016.9, Sep. 27, 1994.
|
Primary Examiner: Powers; Fiona T.
Attorney, Agent or Firm: Connolly and Hutz
Parent Case Text
This application is a continuation of application Ser. No. 08/260,890,
filed Jun. 16, 1994, now abandoned.
Claims
What is claimed is:
1. A monoazo compound conforming to the formula (1)
##STR8##
where M is hydrogen or an alkali metal;
R.sup.1 is hydrogen;
R.sup.2 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon
atoms;
R.sup.3 is hydrogen, halogen, alkyl of 1 to 4 carbon atoms or alkoxy of 1
to 4 carbon atoms;
Y is vinyl or is ethyl which contains in the .beta.-position a substituent
which is eliminable with alkali to form a vinyl group;
p is 1 or 2;
the one --SO.sub.3 M group is attached to the naphthalene ring para or meta
to the amino group.
2. A monoazo compound as claimed in claim 1, conforming to the formula
##STR9##
where M is hydrogen or an alkali metal.
3. A process for dyeing or printing hydroxy- and/or carboxamido-containing
material, by applying a dye to the material and fixing the dye on the
material by means of heat or with the aid of an alkaline agent or by means
of both measures, which comprises the step of employing as a dye a monoazo
compound of claim 1.
4. A process for dyeing or printing hydroxy- or carboxamido-containing
material, comprising the steps of applying a monoazo compound as claimed
in claim 1 to a hydroxy- or carboxamido-containing material, and fixing
the monoazo compound to the material.
5. A process as claimed in claim 2, wherein the material is fiber material.
6. A process as claimed in claim 3, wherein the hydroxy- and/or
carboxamido-containing material is fiber material.
Description
U.S. Pat. Nos. 4,649,193 and 5,097,021 disclose monoazo dyes containing an
amino-substituted fluorotriazine radical in the coupling component and a
fiber-reactive radial of the vinyl sulfone series in the diazo component.
It is true that these dyes have good fiber-reactive and application
properties, but the practice of dyeing with fiber-reactive dyes requires
in addition improvements in the quality of the properties of such dyes and
of the dyeings and prints obtainable therewith and similarly an improved
economy of the dyeing process involved in their use. There consequently
continues to be a demand for novel fiber-reactive dyes whereby the art can
be advanced.
The present invention now provides novel monoazo compounds having
fiber-reactive properties, which conform to the formula (1)
##STR2##
where
M is hydrogen or an alkali metal, such as sodium, potassium or lithium;
R.sup.1 is hydrogen or sulfo;
R.sup.2 is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and in
particular methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and in
particular methoxy, sulfo, hydroxy, halogen, such as chlorine, bromine and
fluorine, or carboxy, preferably hydrogen, methyl, methoxy or ethoxy;
R.sup.3 is hydrogen, halogen, such as chlorine and bromine, alkyl of 1 to 4
carbon atoms, such as ethyl and in particular methyl, or alkoxy of 1 to 4
carbon atoms, such as ethoxy and in particular methoxy, preferably
hydrogen, methoxy or ethoxy;
Y is vinyl or is ethyl which contains in the .beta.-position a substituent
which is eliminable with alkali to form a vinyl group;
p is 1 or 2;
the one --SO.sub.3 M group is attached to the naphthalene ring para or meta
to the amino group.
The monoazo compounds of the formula (1) can be present in the form of the
free acid as well as in the form of their salts. They are preferably
present in the form of their salts and preferably used in the form of
their salts for dyeing and printing hydroxy- and/or carboxamido-containing
materials, in particular fiber materials.
In the formula (1) and also in the formulae given hereinafter, the
individual symbols can have, within the scope of their definition,
meanings identical to or different from one another.
Alkali-eliminable substituents in the ethyl group of the radical Y include
for example sulfato, thiosulfato, phosphato, alkanoyloxy of 2 to 5 carbon
atoms, such as acetyloxy, benzyloxy, sulfobenzyloxy, p-toluenesulfonyloxy,
halogen, such as chlorine, and dialkylamino having alkyl radicals of in
each case 1 to 4 carbon atoms, such as dimethylamino and diethylamino,
hereof preferably thiosulfato, acetyloxy and in particular sulfato.
Similar preference is given to Y as vinyl.
The groups "sulfo", "carboxy", "thiosulfato", "phosphato" and "sulfato"
include not only the acid form thereof but also the salt form thereof.
Accordingly, sulfo groups are groups conforming to the formula --SO.sub.3
M, thiosulfato groups are groups conforming to the formula --S--SO.sub.3
M, carboxy groups are groups conforming to the formula --COOM, phosphato
groups are groups conforming to the formula --OPO.sub.3 M.sub.2, and
sulfato groups are groups conforming to the formula --OSO.sub.3 M, in each
of which M is as defined above.
Diazo components conforming to the radicals of the formula (2)
##STR3##
in the monoazo compounds of the formula (1) include for example
4-(.beta.-sulfatoethylsulfonyl)phenyl,
4-(.beta.-thiosulfatoethylsulfonyl)phenyl, 4-vinylsulfonylphenyl,
4-(.beta.-chloroethylsulfonyl)phenyl,
3-(.beta.-sulfatoethylsulfonyl)phenyl, 3-vinylsulfonylphenyl,
2-methoxy-5-(.beta.-sulfatoethylsulfonyl)phenyl,
2-methoxy-5-(.beta.-thiosulfatoethylsulfonyl)phenyl,
2-methoxy-5-vinylsulfonylphenyl,
4-methoxy-3-(.beta.-sulfatoethylsulfonyl)phenyl,
4-methoxy-3-vinylsulfonylphenyl,
2,5-dimethoxy-4-(.beta.-sulfatoethylsulfonyl)phenyl,
2,5-dimethoxy-4-vinylsulfonylphenyl,
2,5-dimethoxy-4-(.beta.-sulfatoethylsulfonyl)phenyl,
2-carboxy-5-(.beta.-sulfatoethylsulfonyl)phenyl,
2-carboxy-5-vinylsulfonylphenyl,
2-sulfo-4-(.beta.-sulfatoethylsulfonyl)phenyl,
2-sulfo-4-vinylsulfonylphenyl, 2,4-disulfo-5-vinylsulfonylphenyl,
2-hydroxy-5-.beta.-sulfatoethylsulfonylphenyl,
2-hydroxy-4-(.beta.-sulfatoethylsulfonyl)phenyl,
3-sulfo-2-hydroxy-5-(.beta.-sulfatoethylsulfonyl)phenyl,
2-bromo-4-(.beta.-sulfatoethylsulfonyl)phenyl and
2,6-dichloro-4-(.beta.-sulfatoethylsulfonyl)phenyl.
The present invention further relates to a process for preparing the
monoazo compounds of the formula (1) according to the invention, which
comprises diazotizing a compound of the formula (3)
##STR4##
where Y, R.sup.1, R.sup.2, R.sup.3 and p are each as defined above, and
coupling the resulting diazonium compound with a compound conforming to
the formula (4)
##STR5##
where M is as defined above.
The diazotization reaction of the compound of the formula (3) takes place
in a conventional manner, for instance in an aqueous medium at a
temperature between -5.degree. C. and +15.degree. C. and at a pH below 2
by means of a strong acid, such as sulfuric acid or hydrochloric acid, and
an alkali metal nitrite. The coupling reaction takes place in aqueous
solution or in an aqueous-organic medium, in which case the organic
solvent portion is water-miscible and inert toward the reactants, for
example acetone, dimethylformamide, dimethyl sulfoxide and
N-methylpyrrolidone. The coupling reaction generally takes place at a
temperature between 0.degree. and 20.degree. C., preferably between
5.degree. and 15.degree. C., and at pH between 2 and 7, preferably between
4 and 6.
The fiber-reactive aniline starting compounds of the formula (3) are
generally known and numerously described in the literature. The starting
compound of the formula (4) used as coupling component, and its
preparation, is known from U.S. Pat. No. 5,097,021 mentioned at the
beginning.
The separation of the compounds of the formula (1) prepared according to
the invention--hereinafter called compounds (1)--from the synthesis
batches is effected by generally known methods either by precipitating
from the reaction medium by means of electrolytes, for example sodium
chloride or potassium chloride, or by evaporating the reaction solution,
for example by spray drying, in which case this reaction solution may have
a buffer substance added to it. The compounds (1) have fiber-reactive
properties and very good dye properties. They can therefore be used for
dyeing hydroxy- and/or carboxamido-containing material, in particular
fiber material, and also leather. Similarly, the solutions produced in the
synthesis of the compounds of the invention can be used for dyeing
directly as liquid preparation, if desired after addition of a buffer
substance and if desired after concentrating.
The present invention therefore also provides for the use of the compounds
(1) for dyeing hydroxy- and carboxamido-containing materials, i.e.
processes for their application to these substrates. Dyeing is to be
understood as including mass coloration, for example polyamide films, and
printing. The materials are preferably used in the form of fiber
materials, particularly in the form of textile fibers, such as yarns, for
example in the form of hanks, packages, and fabrics.
Hydroxy-containing materials are natural or synthetic hydroxy-containing
materials, for example cellulose fiber materials or their regenerated
products and polyvinyl alcohols. Cellulose fiber materials are preferably
cotton but also other vegetable fibers, such as linen, hemp, jute and
ramie fibers; regenerated cellulose fibers include for example staple
viscose and filament viscose.
Carboxamido-containing materials include for example synthetic and natural
polyamides and polyurethanes, in particular in the form of fibers, for
example wool and other animal hairs, silk, leather, nylon-6,6, nylon-6,
nylon-11 and nylon-4.
The compounds (1) can be applied to and fixed on the substrates mentioned,
in particular on the fiber materials mentioned, by the techniques
customary for water-soluble dyes, in particular for fiber-reactive dyes.
For instance, on cellulose fibers they produce from a long liquor by the
exhaust method and by means of various acid-binding agents with or without
neutral salts, such as sodium chloride or sodium sulfate, dyeings having
very good color yields and also excellent color build-up combined with
high degrees of fixation. They are dyed at temperatures between 40.degree.
and 105.degree. C., if desired at temperatures up to 120.degree. C. under
superatmospheric pressure, and if desired in the presence in the aqueous
bath of customary dyeing assistants. One possible procedure is to
introduce the material into the warm bath and to gradually heat the bath
to the desired dyeing temperature and to complete the dyeing process at
that temperature. The neutral salts which speed up the exhaustion of the
compounds (1) can if desired not be added to the bath until after the
actual dyeing temperature has been reached.
The padding process likewise produces excellent color yields with high
degrees of fixation and a very good color build-up on cellulose fibers, on
which fixing can be effected by batching at room temperature or elevated
temperature, for example at up to about 60.degree. C., by steaming or with
dry heat in a conventional manner.
Similarly, the customary printing processes for cellulose fibers, which can
be carried out either single-phase, for example by printing with a print
paste containing sodium carbonate or some other acid-binding agent as well
as the compound (1) and by subsequent steaming at 100.degree. to
103.degree. C., or two-phase, for example by printing with a neutral or
weakly acid print paste containing the colorant and subsequent fixation
either by passing the printed material through a hot
electrolyte-containing alkaline bath or by overpadding with an alkaline
electrolyte-containing padding liquor with a subsequent batching of this
treated material or subsequent steaming or subsequent treatment with dry
heat, produce strong prints with well-defined contours and a bright white
ground. The appearance of the prints is not greatly affected by variations
in the fixing conditions. Not only in dyeing but also in printing, the
degrees of fixation obtained with the compounds (1) are very high.
When fixing by means of dry heat in accordance with the customary thermofix
processes, hot air from 120.degree. to 200.degree. C. is used. In addition
to the customary steam at 101.degree. to 103.degree. C. it is also
possible to use superheated steam and high-pressure steam at temperatures
of up to 160.degree. C.
The acid-binding agents which effect the fixation of the compounds (1) on
the cellulose fibers include for example water-soluble basic salts of the
alkali metals and the alkaline earth metals of inorganic or organic acids
as well as compounds which liberate alkali in the heat. Especially
suitable are the alkali metal hydroxides and alkali metal salts of weak to
medium inorganic or organic acids, the preferred alkali metal compounds
being the sodium and potassium compounds. Such acid-binding agents include
for example sodium hydroxide, potassium hydroxide, sodium carbonate,
sodium bicarbonate, potassium carbonate, sodium formate, sodium
dihydrogenphosphate, disodium hydrogenphosphate, sodium trichloroacetate,
waterglass or trisodium phosphate.
By treating the compounds (1) with the acid-binding agents with or without
heating, these compounds are chemically bonded to the cellulose fibers;
especially the cellulose dyeings have after the customary aftertreatment
by rinsing to remove unfixed portions of the compounds (1) excellent
wetfastness properties, in particular since such unfixed portions are
easily washed off on account of their good solubility in cold water.
The dyeings on polyurethane and polyamide fibers are customarily carried
out from an acid medium. For instance, the dyebath may have added to it
acetic acid and/or ammonium sulfate and/or acetic acid and ammonium
acetate or sodium acetate in order to bring it to the desired pH. To
achieve a usable levelness of the dyeing, it is advisable to add customary
leveling aids, for example based on a reaction product of cyanuric
chloride with three times the molar amount of an aminobenzenesulfonic acid
and/or an aminonaphthalenesulfonic acid or based on a reaction product of
for example stearylamine with ethylene oxide. Generally the material to be
dyed is introduced at a temperature of about 40.degree. C. into the bath,
agitated therein for some time, the dyebath is then adjusted to the
desired weakly acid, preferably weakly acetic acid, pH, and the actual
dyeing is carried out at a temperature between 60.degree. and 98.degree.
C. However, the dyeings can also be carried out at boiling point or at
temperatures up to 120.degree. C. (under superatmospheric pressure).
The dyeings and prints prepared with the compounds (1) are notable for
bright shades. Especially the dyeings and prints on cellulose fiber
materials have, as mentioned, in addition a high color strength, good
lightfastness and very good wetfastness properties, such as wash, milling,
water, sea water, cross-dyeing and perspiration-fast properties, also good
fastness to pleating, hot pressing and rubbing.
Of particular note are the high degrees of fixation achievable with the
dyes of the invention on cellulose fiber materials, which can be above 90%
in the case of printing processes and pad-dyeing processes. A further
advantage of the compounds (1) is the ease of washing off the portions
which have not become fixed during printing or dyeing, as a result of
which the washing of the printed or dyed cellulose fiber materials can be
accomplished with low quantities of wash liquor with or without an
energy-saving temperature regime during the washing process.
The Examples which follow illustrate the invention. Parts and percentages
are by weight, unless otherwise stated. Parts by weight relate to parts by
volume as the kilogram relates to the liter.
The compounds described in the Examples in terms of a formula are indicated
in the form of the free acid; generally they are prepared and isolated in
the form of their alkali metal salts, such as lithium, sodium or potassium
salts, and used for dyeing in the form of their salts. Similarly, the
starting compounds and components mentioned in the form of the free acid
in the following Examples, in particular Table Examples, can be used in
the synthesis as such or in the form of their salts, preferably alkali
metal salts.
The absorption maxima (.lambda..sub.max) in the visible region reported for
the dyes of the invention were determined in aqueous solution using their
alkali metal salts. In the Table Examples the .lambda..sub.max values are
given in parenthesis in the hue column; the wavelength unit is nm.
EXAMPLE 1
To a pH 6 solution of 50.1 parts of the starting coupling component
1-(2'-morpholino-4'-fluoro-1',3',5'-triazin-6'-yl)amino-3,6-disulfo-8-hydr
oxynaphthalene in 500 parts of water is slowly added with thorough stirring
over about 10 minutes a conventionally prepared aqueous, acidic diazonium
salt suspension of 28.1 parts of 4-(.beta.-sulfatoethylsulfonyl)aniline,
and the coupling reaction is carried out at a temperature from 10.degree.
to 15.degree. C. while maintaining a pH from 4 to 5. After about one hour
the pH of the reaction batch is adjusted to 6 and the monoazo compound of
the invention is isolated in a conventional manner, for example by spray
drying or by salting out with sodium chloride.
The azo compound of the invention has, written in the form of the free
acid, the formula
##STR6##
The monoazo compound of the invention has very good fiber-reactive dye
properties and dyes the materials mentioned in the description, in
particular cellulose fiber materials, such as cotton, by the application
and fixing techniques customary in the art for fiber-reactive dyes in
bright red shades having good fastness properties, of which in particular
the good light and water fastness properties can be singled out.
EXAMPLES 2 TO 19
The following Table Examples describe further novel monoazo compounds
conforming to the formula (A)
##STR7##
(where M is as defined for the formula (1)) in terms of their components.
They can be prepared in the manner of the invention from the starting
compounds evident from the formula (A) (the diazo component D-NH.sub.2
conforming to the aniline compound of the formula (3), cyanuric fluoride,
morpholine and 1-amino-3,6- or -4,6-disulfo-8-hydroxynaphthalene). They
have very good fiber-reactive dye properties and dye the materials
mentioned in the description, in particular cellulose fiber materials, in
the hue indicated in the particular Table Example (here for cotton) in
high color strength and good fastness properties.
______________________________________
Azo compound of formula (A)
Position
Example D of --SO.sub.3 M
Hue
______________________________________
2 4-Vinylsulfonylphenyl
meta red
(516)
3 3-(.beta.-Sulfatoethyl-
meta red
sulfonyl)phenyl (514)
4 2-Sulfo-4-(.beta.-sulfato-
meta red
ethylsulfonyl)phenyl (510)
5 2-Methoxy-5-(.beta.-sulfato-
meta reddish
ethylsulfonyl)phenyl violet
(540)
6 2-Hydroxy-5-(.beta.-sulfato-
meta reddish
ethylsulfonyl)phenyl violet
(538)
7 2,5-Dimethoxy-4-(.beta.-sulf-
meta reddish
atoethylsulfonyl)phenyl violet
(537)
8 2-Methoxy-5-methyl-4-
meta red
(.beta.-sulfatoethyl- (534)
sulfonyl)phenyl
9 2-Chloro-5-(.beta.-sulfato-
meta red
ethylsulfonyl)phenyl (512)
10 2-Carboxy-5-(.beta.-sulfato-
meta red
ethylsulfonyl)phenyl (513)
11 4-Vinylsulfonylphenyl
para red
(513)
12 3-(.beta.-Sulfatoethyl-
para red
sulfonyl)phenyl
13 2-Sulfo-4-(.beta.-sulfato-
para red
ethylsulfonyl)phenyl
14 2-Methoxy-5-(.beta.-sulfato-
para red
ethylsulfonyl)phenyl
15 2-Hydroxy-5-(.beta.-sulfato-
para red
ethylsulfonyl)phenyl
16 2,5-Dimethoxy-4-(.beta.-
para red
sulfatoethylsulfonyl)-
phenyl
17 2-Methoxy-5-methyl-4-
para red
(.beta.-sulfatoethyl-
sulfonyl)phenyl
18 2-Chloro-5-(.beta.-sulfato-
para red
ethylsulfonyl)phenyl
19 2-Carboxy-5-(.beta.-sulfato-
meta red
ethylsulfonyl)phenyl (513)
______________________________________
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